Lubricant comprising gem-structured organo compound

ABSTRACT

Polyolefins, paraffins and polar compounds containing a gemstructured hydrocarbon &#39;&#39;&#39;&#39;backbone&#39;&#39;&#39;&#39; are useful as traction fluids or as components of traction fluids. For example, compositions, useful as additives to libricants (e.g., components of traction fluids), are produced by oxonolysis of polyolefins, particularly of polyisobutylene oligimers containing at least one pair of maximally crowded geminal methyl groups. For example, ozonolysis of the novel polyisobutylenes can produce oxygenated derivatives (ketones, esters, acids, aldehydes, alcohols, etc.) which are useful as components of traction fluids. Blends of the ketones or of mixtures of the acids and ketones with a base oil (e.g., a paraffinic lube, naphthenic lube, a hydrogenated naphthenic or paraffinic lube, polyolefins or hydrogenated polyolefins) are especially useful as traction fluids or as a lubricant for a friction drive or a limited slip differential. Other polar compounds, useful as additives to lubricants or other mineral oil products (e.g., rubber process oils) can be obtained by conversion of polyisobutylene oligimers to polar compounds containing such functional groups as amine, imine, thioketone, amide, thioester, phosphate esters of the alcohols, ether, oxime, acyl halide, acyl hydrazide, chloride, bromide and maleic anhydride adducts. Salts of the carboxylic acids can also be useful as lubricant additives. A tin complex can also be made which has antiwear properties.

United States Patent [1 1 Driscoll et al.

[ 1 Feb. 19, 1974 LUBRICANT COMPRISING GEM-STRUCTURED ORGANO COMPOUND[75] Inventors: Gary L. Driscoll, Boothwyn; Marcus W. Haseltine, Jr.,Brookhaven, both of Pa.

[73] Assignee: Sun Oil Company of Pennsylvania, Philadelphia, Pa.

[22] Filed: June 11, 1971 [21] Appl. No.: 152,303

Related [1.8. Application Data [63] Continuation-in-part of Ser. Nos.135,295, April 19, 1971, and Ser. No. 144,165, May 17, 1971, Pat. No.3,715,313.

[52] US. Cl 252/56 R, 252/33, 252/45, 252/48.2, 252/48.6, 252/52,252/54.6,

252/5l.5 A, 252/51.5 R, 252/79, 260/410.5, 260/4l0.9, 260/533, 260/586 B[51] Int. Cl. Cl0m 1/24, ClOm 1/26 [58] Field of Search... 252/55, 56 S,56 R, 56 D, 79

Primary Examiner-W. Cannon Assistant ExaminerW. Cannon Attorney, Agent,or Firm-G. L. Church, Esq.; J. E. Hess, Esq.; B. A. Bisson, Esq.

Kv 3.86 Kv100 18.l VTF-VI I ASTM-VI 116 [57] ABSTRACT Polyolefins,paraffins and polar compounds containing a gem-structured hydrocarbonbackbone are useful as traction fluids or as components of tractionfluids. For example, compositions, useful as additives to libricants(e.g., components of traction fluids), are produced by oxonolysis ofpolyolefins, particularly of polyisobutylene oligimers containing atleast one pair of maximally crowded geminal methyl groups. For example,ozonolysis of the novel polyisobutylenes can produce oxygenatedderivatives (ketones, esters, acids, aldehydes, alcohols, etc.) whichare useful as components of traction fluids. Blends of the ketones or ofmixtures of the acids and ketones with a base oil (e.g., a paraffiniclube, naphthenic lube, a hydrogenated naphthenic or paraffinic lube,polyolefins or hydrogenated polyolefins) are especially useful astraction fluids or as a lubricant for a friction drive or a limited slipdifferential. Other polar compounds, useful as additives to lubricantsor other mineral oil products (e.g., rubber process oils) can beobtained by conversion of polyisobutylene oligimers to polar compoundscontaining such functional groups as amine, imine, thioketone, amide,thioester, phosphate esters of the alcohols, ether, oxime, acyl halide,acyl hydrazide, chloride, bromide and maleic anhydride adducts. Salts ofthe carboxylic acids can also be useful as lubricant additives. A tincomplex can also be made which has antiwear properties.

15 Claims, 1 Drawing Figure LUBRICANT COMPRISING GEM-STRUCTURED ORGANOCOMPOUND In our parent applications (of which this application is acontinuation-in-part) Ser. No. 135,295 and Ser. No. 144,165, now U.S.Pat. No. 3,715,313, dated Feb. 6,1973 filed Apr. 19, 1971 and May 17,1971, respectively, titled Chemical Reaction Products of Polyisobutyleneand Traction Transmission Containing Lubricant Comprising Gem-StructuredPolar Compound, we disclose the production of a large number ofgem-structured polar compounds, all of which can be useful in practiceof the present invention.

SUMMARY OF THE INVENTION Novel polyolefin oils consist essentially oftrue isobutylene oligimers. Such oligimers are gemstructured, havecrowded geminal methyl groups and are further described hereinafter.Substantially pure olefins of a single carbon number can be obtained asdistillate fractions of such oils. The fractions or the oils are usefulas lubricants (as for traction drives) and can be converted, byhydrogenation or other well known reactions, into gem-structuredparafi'ms or polar compounds, which are useful as lubricants orcomponents of blended lubricants.

More generally, novel polyolefin oils of monomers of the formula R (ll-1:43, 1'1.

wherein R is CH and C H and R, is an alkyl group of from one to carbonatoms, have exceptionally high viscosity indices and high coefficientsof traction and consist essentially of unisomerized, true oligimers,such as true polyisobutylene oligimers (e.g., C l-l C 1-1 C 11, C l-1The novel oils are useful as electrical oils, as chemical intermediatesor as tractants (i.e., as traction fluids or as components of tractionfluids). The hydrogenated oils are novel and especially useful astractants, particularly when hydrogenated to a bromine number less than10 (more preferably, less than five). The unique character of thesenovel oils, whether olefin and/or paraffin, can be proved by acombination of gas chromatography and nuclear magnetic resonancespectroscopy (NMR). These olefins, and the paraffins produced byhydrogenation thereof, are characterized by crowded" and stericallyhindered geminal methyl and isolated methylene groups. The individualspecies in the range of C to C can be separated from the whole oil byvapor phase chromatography. One such novel polyolefin oil having an ASTMviscosity index greater than 85, consists essentially of monoolefins ofcarbon numbers C C C C and C and having repeating isobutylenestructures.

In general, improved traction fluids and components of traction fluidscan be obtained by putting a polar group on a gem-structured hydrocarbon(such as the gem-structured polyisobutylenes), preferably, the compoundcontains no aromatic or olefinic unsaturation. The resulting polarmolecular appears to be more strongly attracted to metal surfaces(compared to the parent hydrocarbon) and thus produces highertracformula:

R R Clixl b-: (CH2) n -Y CHI L R2 lu wherein n is an integer from l30, nis 0 or 1, R, R and R are one or a combination of the followingradicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,isopentyl, neopentyl, cyclohexyl, methylcyclohexyl, indanyl,hydrindanyl, cyclohexylindanyl, cyclohexyl hydrindanyl; and where Ywould be any of the following functional groups: ketone, carboxylicacid, acid salts, ether, alcohol, ester, acyl halide, acyl hydrazide,mercaptan, epoxy, thioester, thiolester, thioether, phosphate (includingcoesters), phosphite (including coesters), sulfate, sulfite, sulfonate,halide, oxime, imine, amide, amine or maleic anhydride adduct. More thanone functional group can be present in a given molecule (e.g., imine andamine). Also, the indanyl compounds and/or their cyclohexyl moieties,may be C lower alkyl-substituted, as for example, with a methyl group.Tin complexes, as hereinafter described, are also polar compounds withinthe scope of this invention.

In the above described polar compounds, the following structuralformulae represent the various indicated functional groups:

Ketone includes 0 ll .R3

Carboxylic acid includes l WWW... l-rbzQflm Alcohol includes OH --OH and(:J-R3

Ester includes O AORa Thiolester includes coester) includes Other usefulphosphorus containing radicals include Halide includes OX2 X 0X: CH;

l mideiiieludes where n" is aninteger from 1 to 12,

Amine includes and any radical which can be obtained by reduction of theamide (as with hydrogen in the presence of Raney Nickel in a solvent,e.g,, ethanol).

In the above structures, R and R can be an alkyl where n, n and Y are aspreviously describ edf group having one to seven carbon atoms or acyclic or alkyl-substituted cyclic hydrocarbon radical which can besaturated, olefinic or aromatic (and preferably saturated), and includes(but is not limited to) the radicals described hereinabove as R, R and RR R and R are hydrogen or any of the radicals or groups described for Rand R R is methyl or hydrogen. R R R R and R when on the same molecule,can be the same radical or different radicals.

A preferred class of polar compounds coming within the above-describedstructural formula is obtained from the true polyisobutylene oligimers,or the other vinylidene polymers, described more fully hereinafter, bysuch chemical reactions as those of the examples herein or byconventional organic reactions used to make polar derivatives ofoleflns. With the polyisobutylene oligimers, these polar compounds canbe described by the formula Such polar compounds are particularly usefulas tractants when added in major (e.g., 50-90 volume percent) quantitiesor minimum effective amounts (e.g., 1 percent, more preferably 3percent, and typically at least 6 percent) to such base oils asparaffinic lubes (preferably solvent refined and/or dewaxed), naphtheniclubes (preferably naphthenic acid free), polyolefin fluids and synthetic(e.g., see US. Pat. No. 3,287,259) naphthenic lubes. All of theabove-referred to base oils can be partially or fully hydrogenated toimproved chemical and/or thermal stability and to permit longer periodsof high traction under use conditions. Particularly useful lubricantscomprise such a hydrogenated base oil which contains less than 5 weightpercent of gel aromatic compounds and less than 10 weight percent ofolefins and which also contains from 0.520 percent of a gem-structuredpolar compound, preferably, corresponding to the above formula.

In one embodiment, the present invention involves lubricant compositionscomprising chemical compounds which can be produced by the action ofvarious chemical reagents on the polyolefins or polyolefin oils. Similarreactions can be performed on other gemsubstituted olefins to obtain thepolar component of the present invention. Such compounds are useful aslubricant additives, particularly lubricants for tractive drives,friction drives and limited slip differentials.

One typical toric traction transmission is that described in Hewko etal., Tractive Capacity and Efficiency of Rolling Contacts," Proceedingsof the Symposium 0n Rolling Contact Phenomena, Elsevier Amsterdam, 1962,pp. 159l6l.

Circulation of the lubricant throughout the drive unit can beaccomplished by spray lubrication or by splash effect. In a furtherembodiment, the lubricant is applied in mist or aerosol form. For mistlubrication, the lubricant can contain, to improve reclassificationand/or reduce stray mist, an effective amount (e.g., 0.012 weightpercent polymer) of a polymeric additive selected from one or a mixtureof acrylic, methacrylic,

5 olefin (e.g., isobutylene) and styrene (e.g., a-methylstyrene)polymers having a viscosity average molecular weight in the range ofl0,000-2,000,000 (preferably 100,000 to 500,000). Such additives aredescribed in the prior art. Of the above noted polar additives the morepreferred are the polyolefins and thepolar polyolefins (e.g.,poly(methyl methacrylate)).

For example, one embodiment of the invention is a traction drivecomprising at least two relatively rotatable members in torquetransmitting relationship, the tractive surfaces of said members havingdisposed thereon a tractant composition containing at least one weightpercent, preferably, at least 5 percent of an oxygen-containing chemicalcompound of a branched ole fin hydrocarbon having 12 to 120 carbon atoms(more preferably 20-80), said olefin hydrocarbon having the formula:

CH: CHr-( I wherein n is an integer from 0 to 29 inclusive (morepreferably 2-40), and wherein Z is:

For example, such compound is produced when said olefin is split at thedouble bond to produce two fragments, each said fragment having acarboxyl group at the site of the original attachment. Other compoundscan be produced by further reaction of one of said frag ments, saidreaction involving either further fragmentation (e.g., decarboxylation),further oxidation, or both.

or when Z is (B), said compounds can be produced by the reaction:

or when Z is (D) such compounds can be produced by the reaction:

or when Z is (E) said compound is produced by at least one of thereactions:

. One class of preferred oxygen con taining compounds in the presentinvention contain at least 1 1 carbon atoms (more preferred at least 15)and have the structural formula where n is an integer from O to 29inclusive and wherein Z is 'lypicallyfcompositions can be ob tairEdT/Hieh contain -99 weight percent of one or a mixture of suchoxygen-containing compounds having a polyisobutylene backbone.

Epoxides can be made from any of the abovedescribed olefins by reactionof the olefin with 30-95 percent (e.g., percent) hydrogen peroxidepreferably in the presence of M00 catalyst.

The substituted p olybutene components of the present invention areusually liquids and have good solubility in petroleum oils. Therefore,these derivatives can be especially useful as lubricant additives or asaddi tives to other oils, or petroleum products (such as rubber processoils, hydraulic fluids, fuels, refrigeration oils, textile machinerylubricants, coolant for a nuclear reactor, paints, etc.). By choice ofthe molecular weight (or viscosity) of the polyolefin starting material,the derivatives can be tailored to a desired viscosity or molecularweight.

An important requirement of a traction fluid for use in such anautomotive transmission system is that it not only have good tractionproperties,but also be a good lubricant for the differential gear anddifferential ball, and a good lubricant for the rollers and races.Although such a traction fluid could also be used as the hydraulic fluidin the toric unit, if a hydraulic fluid of low traction (e.g., high VI)is used, it is preferred that the hydraulic fluid contain an indicatormeans, such as a distinctive dye, so that leakage of the hydraulic fluidinto the main body of the drive unit can be detected by inspection ofthe main body of traction fluid, such as by a dip-stick arrangement.

To prevent loss of fluid by vaporization and to insure againstintroduction of contaminants into the fluid, the transmission systemshould be fully enclosed and well sealed. With the more volatile fluids,the seals and system should be capable of withstanding pressure exertedby the vaporized portion of the fluid at operating temperatures.

DESCRIPTION OF THE DRAWING The accompanying drawing is typical of avapor phase chromatogram, in the C -C region, of a novel polyisobuteneoil of the present invention, and, by nearly baseline resolution (thebroken line is the base line), indicates the very minor content thereinof cracked, isomerized or other non-isobutene oligimer species. Thevapor phase chromatogram of the same oil after hydrogenation will alsobe similar to that of the figure with respect to the virtual base lineresolution.

Each peak in the drawing is produced by a unique hydrocarbon species(e.g., C characterized by maximally crowded and sterically hinderedgeminal methyl and isolated methylene groups.

Vapor phase chromatograms of commercially available polybutene oils showthat such oils do not consist essentially of true oligimers of isobutenebut contain appreciable amounts of virtually all of the carbon numberspecies which could be present within the carbon number range of theoil. For example, a commercially available polybutene oil produceddistinct VPC peaks within the C C range which could be identified as C CC C C etc. This oil also had far from base line resolution (i.e., anenvelope), thus, indicating the presence of many isomeric forms of theother possible carbon number species (e.g., C C C The novelpolyisobutylene and hydrogenated polyisobutylene oils of the presentinvention have a higher viscosity index (usually at least percenthigher) than oils of the same viscosity at 210F prepared frompolyisobutylene by prior art techniques. Although the present inventionincludes oils consisting essentially of isobutene oligimers in the C C.,carbon number range, the more preferred polyisobutene oils describedherein, have a viscosity index in the range of 90-l 30 (typically atleast 95) and consist essentially of true polyisobutene oligimers in the-40 carbon number range. As used herein viscosity index (unlessspecified as ASTM") refers to Viscosity Temperature Function ViscosityIndex (VTF-VI) as determined by the technique of W. A. Wright as setforth in ASTM Bulletin No. 21S, 84, (1956). This value similar to thatobtained by ASTM D 2270 which is reported herein as ASTM-9.

FURTHER DESCRIPTION The proper selection must be made of solvent andcatalyst in order to produce oligimers of the olefin starting materialwith a minimum of the disproportionation and isomerization that arefound in oils of the prior art processes. The solvent serves as a polarsolvent to solvate the intermediate carbonium ions formed during thereaction, and to complex the catalyst to give a catalytically activespecies which remains in the solvent phase. The nitromethane andnitroethane also dissolves appreciable amounts of monomer but little ofthe oils. This last property is believed to be partly responsible forthe narrow molecular weight distribution obtained in the product whenusing these preferred solvents, which results in a more favorableproduct distribution. Suitable solvents for meeting the requirements forthis purpose have been found to be nitromethane, nitroethane,nitropropane, nitrobenzene, benzene, lower alkyl benzenes and mixturesthereof. Suitable lower alkyl benzenes include toluene, the xylenes andethyl benzene. Of these nitro compounds are preferred (with nitroethanebeing the especially preferred solvent). Reasonable yields ofpolyisobutylene oils having KV =1.52O and VTF-VI=-l 15 can be prepared.

The preferred process for the preparation of these {fluids involves theuse of substantially anhydrous stannic chloride as catalysts andnitromethane (or nitroethane) as solvent. However, small amounts ofwater can act as reaction promotors.

The catalyst used in the preferred process (for making oils having anaverage molecular weight up to about 1,000) isstannic chloride. Thestronger Lewis acid catalysts such as aluminum chloride, aluminumbromide, titanium tetrachloride and antimony pentachloride, do not causeany appreciable polymerization of the monomers in nitromethane. Borontrifluoride in nitromethane gives an oil product from isobutene having aviscosity index of about 75. Stannic chloride does not catalyze thepolymerization of these monomers satisfactorily in such solvents asether, water, dioxane, acetic acid, acetone, acetonitrile, aceticanhydride, diethylene glycol monoethyl ether, chloroform, methylacetate, dimethoxyethane, N-methyl-pryrolidione, and

.hexamethylphosphormaide.

This system is operated at low pressure near ambient temperature, giveshigh ratios of product to catalyst consumed, is highly selective forisobutylene while tolerating a wide variety of feed compositions, iseasily controlled to give the desired products, and is well suited forcontinuous recycle operation.

Product isolation involves simple phase separation. The productdistribution is suffciently narrow that simple vacuum topping isrequired so no heavy byproducts are formed. By-product dimer, trimer andtetramer have some commercial uses and are also readily cracked toisobutylene for recycle.

The most important reaction variables are the temperature and the rateof feed relative to the amount of 1 the reaction medium and separatingthe product from the catalyst and solvent; the ratio of solvent toproduct generally is maintained at from 2:1 to 1:2.

The catalyst may be used in an amount equal from 0.1 to 40 volumepercent of the solvent present, and preferably from 1 to 20 volumepercent of the solvent present.

The concentration of the free monomer in the reaction medium isrelatively small and can be controlled by the pressure maintained atgiven temperature for gaseous feeds, and by rate of addition for liquidolefin feeds, thus, controlling the molecular weight of the product.Generally pressures of from about 1 to 275 psi absolute have been foundmost suitable with from 10 to 100 psia being the preferred range.

The feed stock can vary from 5 to 100 percent vinylidene monomer (e.g.,isobutylene), the remainder being any inert hydrocarbons. The presenceof hydrocarbon non-vinylidene compounds is not detrimental since thevinylidene monomers as defined herein are selectively polymerized by thecatalyst system. For instance, the efficiency of isobutene removal frommixtures of isobutene and other butenes and/or butanes depends on theparticular process but is relatively insensitive to small amounts ofimpurities such as air, water, organo-sulfur or organo-nitrogencompounds.

Distillation to produce different oil compositions can give varyingresults depending on the vacuum, the apparatus, the distillation rateand the composition of the. reaction product which is distilled. Undersome conditions, considerable 1 5%) trimer can be left when the oil istopped to 80C, under other conditions little of the trimer or tetramerwill remain. More typically one-third of the tetramer remains in theoil, and two-thirds of the tetramer and nearly all of the trimer areremoved. In addition, distillation is inherently limited by the thermalstability of the oil. At temperatures (of the overhead distillate) from175 to 225C, cracking of the oil can become so severe that the pressurestarts to increase (usually the pressure is less than 1.0 mm Hg.

Vapor phase chromatograph (VPC) scans give good information on therelative amounts of dimer, trimer, etc., up to about C The oils producedby the process may have a number average molecular weight of from 224 toabout 2,000. The preferred product contains principally the tetramer todecamer range. The tetramer in the present case consists predominantlyof a major and a minor component. In the case of isobutene thehydrogenated major tetramer component has the structure:

and the minor component has the structure:

CH: CHa H CH3 CHI-L CH3 This latter type of structure predominates abovethe tetramer (i.e., at pentamer and above). The repeating unit forcomponents of the pentamer and higher oligimers is indicated by thebrackets in the formulae. The higher olefins such as Z-methylbutene-lproduce the corresponding regular structures when oligimerized inaccordance with the previously described process con ditions.

Vinylidene monomers suitable for preparing novel, unisomerized" oligimeroils, by the process described herein, have the formula:

wherein R is CH or C H and R is an alkyl group of from 1 to 10 carbonatoms.

These oligimers are useful in the as produced unsaturated forms aselectrical oils. When the oils are to be used as traction fluids theymay be hydrogenated using a conventional hydrogenation catalyst such asRaney nickel, platinum, palladium or rhodium to improve the oxidativestability thereof. However, the olefinic oils are relatively stable anddo not require further treatment in order for them to be suitable foruse as traction fluids. For most uses such as traction fluid the highermolecular weight product may be left with the tetramer to decamer rangematerial, but the dimers and trimers should be separated therefrom alongwith the monomer. This is readily accomplished by distillation.

The oils as produced by the present process find particular advantage intheir use as traction fluids (particularly in blends with saturatedcyclic compounds) due to their high coefficients of traction andexcellent viscosity-temperature properties. The requirements of atraction fluid are discussed in the US. Pat. Nos. 2,549,377; 3,440,894and 3,411,369. Compounds described in the present application can beincorporated, as additives, to such prior art traction fluids. Exemplarytractive devices in which the traction fluids of the present inventionfind use are disclosed in US. Pat. Nos. 1,867,553; 2,871,714; 3,006,206and 3,184,990.

Additionally these oils find use in caulks and as reactants, electricaloils, etc.

ILLUSTRATIVE EXAMPLES Example 1 i A three-necked, one-liter,round-bottomed flask was equipped with a mechanical stirrer, a gas inlettube (which also serves for intermittent product removal), and a refluxcondenser containing a thermometer which dipped into the liquid layerand was capped with a gas exit tube leading through a mercury bubbler tothe atmosphere. Nitromethane (200 ml.) and stannic chloride (5 ml. l1.15 g.) were added to the flask and the isobutylene flow started. Thereaction was maintained at 3+lC with an ice bath. The rate ofisobutylene addition as 7.2 g/min. which resulted in 8.5 ml/min. ofproduct (density about 0.85) formation. At 20 minute intervals, theisobutylene feed and the stirrer were stopped and the layers permittedto separate. The top oil layer ml.) was removed and the nitromethane(bottom) layer was returned to the reactor with 5 ml. (3 percent ofproduct volume) fresh nitromethane added to compensate for solubilitylosses. After four 20-minute runs, the reaction was stopped. Thecatalyst in the nitromethane layer was readily killed with water withsome production of HCl fumes. No difficulty with an exotherm wasencountered when killing the catalyst.

The combined oil layers (665 ml. including 20 ml. nitromethane) werewashed with water, with 5 percent sodium hydroxide solution, and twicemore with water. A solvent such as pentane or hetane can be added tofacilitate handling.

Although the oil of this example contains all of the novelpolyisobutylene oligimers in the series G -C C f, fractional vacuumdistillation can be used to obtain a fraction relatively pure in a givenoligimer (e.g., C

In the reaction of this example, small amounts of water in the catalystand/or feed material can act as a reaction promoter. lf extremely purematerials are used in the process, a small amount of water can be addedto initiate or hasten the reaction. A lower alcohol (e.g., methanol) oracid (e.g., acetic acid) can also be used as such a promoter. Generally,the reaction rate can be increased (over anhydrous) by addition of 0.ll.5 moles H O per mole of SnCl Polyolefin products, such as that of thisexample, can contain residual tin and chlorine (e.g., 2505,000 ppm Cl).As is discussed in more detail hereinafter, these elements, particularlythe tin, can be present as a metal organic compound which imparts EP(extreme pressure lubricant) properties to the product. However, if onedesires, the chlorine (e.g., 2,000 ppm) can be removed from the productby heating the product with calcium oxide (lime) followed by filtration.Mild catalytic hydrogen treatment (e.g., 200 psi of H 200C, HarshawNl-l04P catalyst) can also be used to reduce the tin and chlorinecontent to very low levels (e.g., Cl from 2,000 ppm to 6 ppm).

The process of the present example can also be used to convert butadieneto trans-l ,4- and 1,2 polybutadienes. This is surprising since priorart cationic catalyst systems convert butadiene to cyclized polymers.

l-Decene can also be polymerized with the catalyst system of the presentexample if AlCl is substituted for SnCl particularly to get high yieldsof a low viscosity oil. Oxygenated derivatives of these poly l-decenescan be obtained by ozonolysis in a similar manner to the process of thenext example.

Example 2 Polyisobutylene oil from Example 1 (260 ml., 221.4 g.) andanhydrous methanol (800 ml.) were placed in a three-necked, 2-liter,round-bottomed flask equipped with a gas inlet tube, a mechanicalstirrer and a reflux condenser. The flask was maintained at about 0C bymeans of an ice bath while an oxygen-ozone stream (5.2 millimoles 0 perminute) was passed through for 150 minutes. After this time the productwas given a hydrolytic work-up, that is distilled water (300 ml.) wasadded and the mixture heated to reflux for 90 minutes. The oil layer wasdiluted with pentane (500 ml.) and successively extracted with about 250ml. of water (twice); 5 percent ferrous sulfate solution; 5 percentsodium carbonate solution; water; 5 percent sodium carbonate solution;and water (twice).

The combined sodium carbonate and water extracts were acidified withconcentrated hydrochloric acid and extracted with ether. After drying,the ether was removed to recover 8 g. (3.6 percent) of an acidicfraction.

The main pentane layer was dried over calcium chlride and the pentaneremoved on a steam bath to recover l94 g. (87.6 percent by weight) ofaneutral fraction. The infrared spectral analysis of this material showedthat it contained mainly carbonyl (aldehyde or ketone) functionalitywith smaller amounts of hydroxyl functionality. Analysis by gas-liquidchromatography 5 showed that the composition of the product wasessentially a repeating pattern of three major components in a givenmolecular weight range. It is possible that other components were notseparated using 6-foot silicone oil columns and 6-foot polyethyleneglycol columns. Several minor components were also detected. Very littleunreacted oil was present. This product will be referred to sometimeshereinafter as PIB-ketone or PlB-ketone, hydrolytic work-up.

Example 3 The neutral product (PIE-ketone) of Example 2 was tested forits traction using a Roxana Four-Ball tester sold by Roxana MachineWorks, St. Louis, Mo. It showed a traction higher than the originalpolyisobutylene (about 85 g. of torque versus about 72 g. initially) andhigher than for commercially available polybutcnes (about 66 g. oftorque). This indicates that the product is useful as a traction fluidor as a component of a traction fluid.

. an... CH3 CH3 CH3 0 5 & ii CHa- I 'CH2 z- I ---CH2 CH:;

CH1 CH3 CH:

4,4,6,6,8,8-hexamethyl-2-nonanone. The two lesser components wereidentified as 1,1,3,3,5,5,7,7-octamethyl-1-octanol and2,2,6,6,8,8-hexamethyl-4-nonanone.

The structural formulae of higher boiling fractions correspond to theabove structures with an additional appropriate number (e.g., up to atotal carbon number of at least about 49 for the ketones and at leastabout 50 for the alcohols) of units inserted after the first t-butylgroup. The PlB- ketone is therefore a mixture containing predominantlyketones (at least about 75 mole percent).

Example The neutral product (50 g.) of Example 2 was dissolved in 200ml. of diethyl ether and reacted with an excess of lithium aluminumhydride (8.0 g.) for 4 hours at reflux. The excess hydride wasdecomposed by reaction with ethyl acetate and 200 ml. of percenthydrochloric acid was added cautiously. The ether layer was extractedtwice with 250 ml. of water, dried over calcium chloride and the etherremoved on a steam bath. The oily product (48 g., 96 percent by weight)was characterized as an alcohol by its infrared spectrum. No carbonylabsorption remained. Its gas-liquid chromatogram showed a repetition oftwo major peaks, the components having the samemolecular weight nolonger being separated by this column (6 feet of silicone rubber).

The alcohols which contain a large non-polar portion and a very polaralcohol portion are referred to sometimes hereinafter as PlB-alcohol andare useful as solvents and especially as components of traction fluidsand as components in solvents for polymers such as polystyrene andpolymethylmethacrylate. They are also useful as intermediates in thepreparation of the corresponding acetate esters.

0 Example 6 The alcohols of Example 5 g.) were mixed with an excess ml.)of acetic anhydride and heated on a steam bath for one hour. Excesswater 100 ml.) was added to decompose the excess acetic anhydride. Themixture was heated for an additional hour. Ether (100 ml.) was added andthe ether layer separated. The ether layer was extracted twice withapproximately 100 ml. portions of water and then dried over calciumchloride. After the ether was removed, an infrared spectrum was obtainedon the remaining 20 g. (100 percent by weight) of oil. The infraredspectrum showed the presence of carbonyl groups (ester) and thesubstantial absence of hydroxyl groups (alcohol). This ester was usefulas a traction fluid, both alone and in blends (as with hydrogenatedpolyolefin oils or hydrogenated paraffinic or naphthenic lubes or withmythetic naphthenes or adamantanes). The ester is also useful as acomponent of a gear lube, especially a lubricant for a limited slipdifferential. Typically blended fluids or lubes can contain in the rangeof l to 95 percent of such an ester and 99-5 percent of one or a mixtureof oils of the parafiinic, naphthenic or polyolefin classes (such oilscan be partially or fully hydrogenated).

Example 7 A solution was prepared in a two-liter flask by mixinghydroxylamine hydrochloride (100 g.), water (600 ml.), 10 percent sodiumhydroxide solution (400 ml.), and ethanol (400 ml.). This mixture wasstirred while the neutral ketone product ml., 34 g.) prepared accordingto Example 2 was added. The resulting mixture was heated and stirred at80C for 30 minutes. The entire mixture was diluted with 1,000 ml. waterand extracted with 500 ml. ethyl ether. The ether layer was extractedtwice more with 500 ml. portions of water. The ether layer was driedover calcium chlroide and the ether removed on a steam bath. Theresulting oil 28 g. (82.4 percent by weight) was found by infraredspectroscopy to contain oxime functions and substantially no unreactedcarbonyl functionality. This oxime is soluble in paraffinic andnaphthenic petroleum oils and is useful as a traction component or as aviscosity stabilizer for oil-extended unvulcanized rubber stock.

Example 8 A three-liter, round-bottomed flask was equipped with a gasinlet tube, a mechanical stirrer and a reflux condenser. This wascharged with acetic acid (1,500 ml.) and polyisobutylene oil (500 ml.)prepared according to Example 1. An oxygen'ozone stream (5 liters perminute, 5.3 millimoles ozone per minute) was passed through the mixturefor 240 minutes. The temperature was maintained in the range of 25 to50C by means of a water bath. The reaction mixture was initially twophases, but became homogeneous near the end of the reaction time.

The crude mixture was then given an oxidative work-up, that is, it washeated to to C and 30 percent hydrogen peroxide solution (500 ml.) wasadded cautiously over a period of 50 minutes. The mixture was thenrefluxed (about 1 10C) for 6 hours. Ether (1,000 ml.) and water ml.)were added and the layers separated after stirring. The ether layer waswashed twice with water and twice with 0.2 percent ferrous sulfatesolution (500 ml. each). The ether layer was next washed with 10 percentsodium carbonate solution (500 ml.) and twice with water (1,000 ml. eachtime). Since the sodium salt of the acid is much more soluble in waterthan in sodium carbonate solution, most of the separation occurs in thetwo water washes. The remaining ether layer was dried over calciumchloride and the ether removed on a steam bath to give the neutralketonic fraction. Gas-liquid chromatography and infrared spectroscopyindicated that the product was similar to the product of Example 2, butmore complex and showing indications of significant isomerizations. Thisneutral fraction amounted to 232 g. (55.0 percent by weight) and ishereinafter sometimes referred to as PlB-ketone, oxidative work-up.

The sodium carbonate extract and the two following water extracts werecombined and made acidic by cautious addition of excess hydrochloricacid and extracted with diethyl ether (500 ml.). The ether layer wasdried over calcium chloride and the ether removed on a steam bath. Theresulting liquid acid fraction weighed 134 g. (32.3 percent by weight)and is hereinafter referred to sometimes as PlB-acid. The infraredspectrum showed the absorbance bands characteristic of carboxylic acidfunctions.

Ten percent PlB-ketone in a hydrogenated solventrefined paraffinic oilyields a torque transmission of 67 grams compared to 58 grams for thehydrogenated oil containing no additives. The PIB-ketone, oxidativework-up produces similar results.

Any of the polar compounds described herein perform as a tractionimproving additive in any petroleum oil (paraffinic or naphthenic),including oils produced by hydrocracking, or any compatible syntheticfluid (silicones, ester oils, polyolefins, fluorinated fluids).

The polar compounds can be used as extreme pressure additives and/orwear additives. The polar end of the molecule is apparently stronglyattracted to the metal surface, resulting in less wear of the surfacedue to the protective action of the gem-structured backbone.

Example 9 The sodium salt of the acidic fraction can be readily obtainedby proceeding according to Example 8 to the first water extractionfollowing the 10 percent sodium carbonate extraction. When these twoextracts were mixed, a phase separated. This can be diluted with diethylether and the phase separated. Drying over calcium chloride and removalof the ether on a steam bath results in a viscous liquid product whichhas an infrared spectrum consistent with a sodium carboxylate.

This product is useful as a detergent, as a surface active agent, and asa solubilizing agent. At least percent diethyl ether can be dissolved inwater containing a few percent of this salt.

The sodium salt can also be prepared directly from the acid and asuitable base under nearly anhydrous conditions. Salts of other metals,e.g., lithium, calcium, magnesium, barium, zinc and cobalt, can also beprepared in a similar manner. Such salts are useful in compoundinggreases, hydraulic oils, lube oils, etc. Such salts (e.g. Na") can beused to increase the viscosity and/or reduce acidity of lubricants,especially lubricants for traction or friction drives.

Example 10 The acidic fraction prepared according to Example 8 ml., 22.6g.), methanol (200 ml.), and 96 percent sulfuric acid ml.) were placedin a 500 ml. roundbottomed flask and refluxed for 6 hours. Water (200 Iml.) and diethyl ether (200 ml.) were added and the layers separated.The ether layer was successively extracted with water, 10 percent sodiumcarbonate, and water using 200 ml. each time. The ether layer was driedover calcium chloride and the ether removed on a steam bath. Theresulting neutral ester product weighed 18 g. (80 percent by weight) andis sometimes referred to hereinafter as PlB-ester. Gas-liquidchromatography showed the repeating pattern to be three major componentsat each general molecular weight level. The repetitions werecharacterized by the fourcarbon CHz unit. Infrared analysis showed theabsorbance expected for ester functionality and the absence of acidfunctionality. v v

The'ester was useful as a traction fluid and as a component of blendedtraction fluids. Particularly useful blended base stock comprises 1 to99 percent of the ester and from 99 to 1 percent of at least onenaphthene or paraffin having an SUS viscosity at l60F in the range of2525,000. Example 1 1 An acid (1 g.) prepared according to Example 8 wasmixed with thionyl chloride (1 ml.) and carefully warmed on a steam bathuntil the bubbling subsided. It was then heated and a nitrogen flowmaintained while the thionyl chloride evaporated. Finally, a wateraspira- Example 12 The acyl halide product of Example 1 l was pouredinto methanol (25 ml.). Water (50 ml.) and diethyl .ether (50 mol.) wereadded and the layers separated.

The ether layer was extracted (once with 5 percent sodium carbonate [50ml.] and twice with water ml. each]). The ether layer was dried overcalcium chloride and the ether removed on a steam bath. The resultingoily product was shown by gas-liquid chromatography and infraredspectroscopy to be identical with the PlB-ester of Example 10.

Example 13 5 An acid (50 g.) prepared according to Example 8 and excess(20 g.) of 85 percent hydrazine hydrate (the remaining 15 percent beingwater) were mixed in a 250 ml. Erlenmeyer flask with magnetic stirring.The mixture immediately became warm. The temperature was then raised byexternal heating to C and excess hydrazine fumed off in awell-ventilated hood. The temperature was maintained at 125C for 2 hoursthen raised to to 210C for a further 2 hours. An infrared spectrum ofthe very viscous material showed that it was substantially converted tothe acyl hydrazide derivative. The product was dissolved in diethylether (400 ml.) and extracted twice with water (500 ml. each time). Manyof these extractions resulted in serious emulsion difficulties. Suchemulsions were broken with concentrated sodium chloride solution, butseparation times of one to two days were still occasionally required.The ether layer was dried over calcium chloride and the ether removed ona steam bath.

The product was very viscous and light orange in color. An infraredspectrum was again determined and showed somewhat sharper bands. Thematerial was especially characterized by absorbances near 3.1M and 6.1M,typical of acyl hydrazides. This hydrazide was different from othersbecause it was liquid, rather than solid, and was soluble in pentane,white mineral oil, and other hydrocarbons, but insoluble in water. Thisis to be contrasted with the hydrazide from oleic acid, which is solidand unsoluble in oil. Adipyl dihydrazide, acetyl hydrazide and benzoylhydrazide are also solids which are soluble in water but insoluble inhydrocarbons. The hydrazide of this example is especially useful as atraction component, or as a viscosity stabilizer in oilextendeduncompounded synthetic rubbers because of these solubility properties.It is also useful as an emulsifying agent and as an antiozonant inrubber.

. Example 14 The acid 10 g.) prepared in Example 8 was dissolved inmethanol (50 ml.) containing added water (1 mol.). Sodium borohydride (3g.) was added in small portions over one hour. Ether (100 m1.) and water(100 ml.) were added and the layers separated. The ether layer wasextracted twice more with water (100 ml. each) and the ether layerdiscarded. The combined water layers were cautiously acidified withconcentrated hydrochloric acid and ether 100 ml.) was added. The layerswere separated. The ether layer was extended with water (100 ml.), driedover calcium chloride and the ether removed. The resulting acid wasconverted to its corresponding ester by the procedures of Examples 1 land 12. Gas-liquid chromatography showed that the middle component ofthe three major components described in Example 8 was considerablyenhanced.

Since it is well known that sodium borohydride will not reducecarboxylic acids under these conditions but will reduce esters, ketonesand aldehydes, it is reasonable to conclude that the center and largestcomponent represents the original acidic component and the other peaksrepresent other carbonyl components not separated due to the previouslymentioned strong solubilizing power of the sodium salt of the carboxylicacid.

Example The neutral ketone (10 g.) prepared according to Example 2 wasslowly added to 85 percent aqueous acetic acid (100 ml.) containingchromic acid (2 g.) heated on a steam bath to around 90C. This was leftfor 2 hours with occasional shaking. Then water (200 ml.) and ether (200ml.) were added. The ether layer was extracted with water, 10 percenthydrochloric acid, 10 percent sodium hydroxide solution and twice withwater. It was then passed over a 3 foot X 1 inch column ofchromatographic grade alumina. The ether used for this elution wasremoved to leave a product of a dissolved salt of chromium (Ill).Gas-liquid chromatographic analysis showed that the resulting productwas a substantially purified form of the indicated ketone:

The paramagnetic complex, europium (lll) 2,2,6,6-tetramethylheptanedionate [tris(dipivalomethanato)- europium (lIl)],reffered to hereinafter as Eu(DPM) can be used as an NMR shift reagentand, thus, provides a means of characterizing oxygenated compounds, suchas those of Example 4 and Example 15. Eu( DPM can be used to produceselective proton resonance shifts which accentuate chemical shiftdifferences between geminal methyl and between isolated methylenegroups, as in the highly branched alcohols and ketones.

Example 16 The reaction product of Example 1 contains substantialamounts of tin and chlorine. More probably, the tin and chlorine arechemically combined, in a highly soluble and compatible form, with oneor more isobutylene oligimers. In any event, the recoveredpolyisobutylene oil can also contain such tin and chlorine. Such a noveltin and/or chlorine containing polyisobutylene oil has improved antiwearproperties (e.g., a 4-ball tester wear-scar in the order of 0.4 to 0.6mm. compared to about 0.75 mm. for a solvent refined paraffinic lube ofcomparable viscosity). Chemical derivatives (such as those of thepreceeding Examples 2 to 6 and 10) can also exhibit improved antiwearproperties, which can be caused in whole or in part by inclusion of suchtin and chlorine or, perhaps, the improved antiwear properties may be,in whole or in part, an inherent property of said derivative.

An antiwear additive (e.g., for incorporation in conventional naphthenicdistillate oils, hydrorefined oils, hydrocracked oils, white oils,solvent refined paraffiuic oils or mixtures of two or more such oils)can be obtained from such reaction products (or tin and chlorinecontaining oils) by such means as extraction with a solvent (preferablyacetone) for the presumed organo tinchlorine complex. Preferred solventscomprise acetone, ethanol, methanol, methyl ethyl-ketone, dimethylforrnamide, furfural, nitromethane, nitroethane, and the like; that is,solvents which will not dissolve the oil but will dissolve the morepolar complex. Readily detectable antiwear protection is provided bysuch additives at concentration levels which impart 100 parts of tin permillion parts of oil, with a typical range being 50 ppm. to 10 weightpercent of tin.

Therefore, one aspect of the present invention is novel lubricating oiladditives comprising the tincontaining products of the polymerization ofisobutylene using stannic chloride catalyst, such polymerizations beingcarried out between C and C at a pressure from 0-250 psia. Theseadditives can contain from 0.005 to 50 weight percent tin.

These compositions can also be used as additives to fuels (e.g., dieseloil, gasoline and jet fuel) to prevent wear.

A one-liter round bottom three-necked flask equipped with a mechanicalstirrer and a thermometer was charged with nitroethane (200 ml.) andstannic chloride (5 ml. l 1.2 g.). The temperature was maintained at 30Cwith an external ice bath while isobutylene was bubbled in for 1 hour.After this time the stirring was stopped and the upper oil layer (530ml.) was separated from the lower nitroethane layer ml.). After waterwashing and drying over calcium chloride, the oil layer was distilled toget a fraction boiling up to 82C at 2 mm. Hg (which was discarded), afraction boiling from 82C at 2 mm. Hg to C at 1 mm. Hg,KV o F =18.14cSt.

In the same equipment, except that the flask had a volume fo 500 ml.,the charge was nitromethane (200 ml.) and stannic chloride (20 ml. 44.6g.). The temasture was maintained at 1 5C for ff minutes at the samerate of isobutylene addition used before. The upper layer was washedwith water and dried over calcium chloride. It was then distilled toremove distillate boiling up to 80C at 1 mm. Hg pressure. The remain ingoil residue (KV- o F 46.74 cSt) was saved for wear testing.

In the same equipment, the charge was nitromethane (200 ml.), pentane(200 ml.), stannic chloride (20 ml. 44.6 g.) and water (150microliters). The temperature was maintained at10C for one hour at thesame rate of isobutylene feed. The mixture was allowed to stir for anadditional 30 minutes. The oil product was washed and dried over calciumchloride. The pentane was removed under aspirator vacuum and the productdistilled to a boiling point of 80C at 1 mm. Hg, the small amount of thedistillate being discarded. The bottoms (KV o F about 420 cs) yield wasabout 500 ml. It contained 4.5 percent tin and 2.5 percent chlorineafter filtration through distomatious earth at 80 to 100C. This oil (100ml.) was extracted three times with acetone (25 ml. each time). Theextracts were combined and the acetone was removed by heating to 90Cunder a stream of nitrogen. The extracted oil, about 90 ml., and theextract, 10 ml. had similar viscosities. The initial oil had 4.6 percenttin; the extracted oil had 1 percent tin; and the extract 33 percenttin. This oil and the extract, as with the other tin-containing productsreferred to above, can be added to lubricants to impart antiwearproperties thereto.

Example 17 A polyisobutylene oil (33 g., about 1 mole) preparedaccording to Example 1 was dissolved in carbon tetrachloride (150 ml.)and bromine was added dropwise to the stirred solution. White fumescould be seen above the reactor. These fumes tested very acidic on moistindicator paper. The fumes, caused by the presence of hydrogen bromide,indicate that a substitution reaction was occuring as well as theexpected addition reaction. Bromine addition was continued until thecolor of unreacted bromine persisted for several minutes of warming. Thetotal amount of bromine added was about 40 grams or 2 /2 times thetheoretical amount needed for the addition reaction. The CCL, layer wasextracted twice with water, once with sodium bisulfite solution (toremove the excess bromine) and twice more with water. The CCl wasremoved by heating on a steam bath to leave a light brown oil, sometimesreferred to hereinafter as FIB-bromide. lts infrared spectrum showed CH,CC and CBr functionality. The oil was a source of active halogen and wasfound to be useful as an anti-weld component of cutting oils. The yieldwas 60 grams of isolated product oil. The chloride can also be preparedby a similar reaction of the olefin with chlorine and is useful as an EPadditive, particularly in lubrication of a traction or friction drive.PlB-bromide (or individual bromated polybutenes) can be reacted withdiamines or other polyamines (e.g., at reflux in dimethyl formamidesolvent) to form an imine-amine, those of the following structure beingespecially good traction fluid components:

Preferably n is 2-l0 (e.g., 2) and n is l- (e.g., 3). A preferred polartractant is 5,5,7,7,9-hexamethyl-4- azadecylamine.

Example 18 Polyisobutylene oil (330 g., about 1 mole) prepared accordingto Example 1 was mixed with maleic anhydride (100 g., about 1 mole) andheated to 225C (attained over a period of about 1.5 hours) in a stirredflask equipped with a reflux condenser. The reaction could be followedby infrared spectroscopy. Over a period of time, the absorbance due tothe double bonds in the oil disappeared. At the same time, theabsorbances due to maleic anhydride diminished and new bands appeared.These still indicated an anhydride functionality. After 6 hours, thereaction was stopped and allowed to cool and stand overnight. Themixture developed some solid content during this time. Pentane (500 ml.)was added and the mixture cooled in ice to case additionalprecipitation. The solids were filtered from the mixture on a porousglass filter using a small amount of cold pentane to wash the solids.The white solid weighed 23 g. when dry and had an infrared spectrumwhich showed it to be unreacted maleic anhydride. The pentane wasremoved on a steam bath to give a very viscous, sticky oil. The yieldwas 400 g. The infrared spectrum of the derivatized oil showed a littleremaining maleic anhydride, with a large amount of other anhydride,probably polyisobutylene succinic anhydride. This viscous oil was usefulas a detergent, as an antiwear agent and as an intermediate in theproduction of a hydrazide" derivative.

Example 19 The product of Example 24 (42 g., about 0.1 mole) was stirredand 85 percent hydrazine hydrate (1 1.8 g., about 0.2 mole) was added.The temperature of the mixture rose to about 80C during the addition.The resulting mixture was stirred for 1 hour, then heated to 150C whilenitrogen was passed through the mixture for 2 hours. This removed theexcess hydrazine and converted the portion present as a salt intohydrazine. The resulting mixture was dissolved in ether and extractedwith water to remove hydrazine and its salts. The ether was removed toleave a very viscous, sticky, yellow-brown oil (33 g. or percent oftheory). The infrared spectrum of this material was similar to theinfrared spectrum of other acyl hydrazides. It is useful as a componentof a traction fluid.

Example 20 Polyisobutylene oil, produced as in Example 1, wasfractionally distilled, at atmospheric pressure, to obtain a productwhich contained at least weight percent of the C isobutylene oligimer(i.e., tetraisobutylene). This predominantly C fraction boiled in therange of 190 to 245C and over volume percent boiled at 240C. Analysis byvapor phase chromatography showed that this predominantly C fractioncontained less that 10 weight percent C oligimer and less than 10 weightpercent of the C and higher oligimers.

Example 21 Twenty-two hundred and sixty ml. of winter strained lard oilwere blended with 400 ml. of tetraisobutylene (prepared as in Example20) in a 5-liter kettle equipped with a vibromixer. The mixture washeated to 250F and the vibromixer operated at maximum speed. Sulfur (239g.) was added and the temperature of the mixture raised to 375F for 2hours. The mixture was then cooled to 200F and air was bubbled throughthe mixture by means of a glass tube at a moderate rate (below that atwhich splashing and agitation take place) for 1 hour. The resultingsulfurized oil was analyzed and found to contain 8.23 percent sulfur. A10 gram portion of the sulfurized oil was dissolved in g. ofacommercially available solvent refined paraffinic lube having aviscosity at 210F of 40.45 SUS, and ASTM viscosity index of 104 andcontaining 12 percent aromatics (by ASTM D2007). The oil solutionremained clear with no separation after being tested at 36F overnightand for 1 week at room temperature.

Example 22 Winter strained lard oil (2550 ml.) was blended with 450 ml.of 80+ percent pure triisobutylene (prepared by a distillation similarto that used in Example 20 but at a lower temperature), in a 5-literkettle equipped with a vibromixer. The mixture was heated to 250F andthe vibromixer operated at maximum speed. These conditions weremaintained while 266 g. of sulfur were added over a period of 30minutes. The temperature was raised to 375F for 2 hours. The mixture wasthen cooled to 200F for 1 hour and air was bubbled through the mixtureby means of a glass tube at a moderate rate below that at whichsplashing takes place. The resulting sulfurized oil was analyzed andfound to contain 8.6 percent sulfur as based on the total composition. Aten gram portion of the sulfurized oil was dissolved in 100 g. of thesolvent refined paraff'mic oil described in Example 27. The oil solutionremained clear with no separation after being tested at 36F overnightand for 1 week at room temperature.

Example 23 A useful lubricant for a controlled-slip differential, andwhich is also useful for lubrication of a traction drive transmission,comprises a blend of the following (all hydrogenations are to at least98 percent saturation):

KV210F. KVIF. Volume Component (c.s.) (c.s.)

7.0 Hydrogenated Cosden SH06 I104 124 Polybutcne 28.0 HydrogenatedCosden SH 33.5 744 Polybutene 31.6 Hydrogenated Poly a-Methyl 23.0 2463Styrene 2L0 Hydrogenated Poly aMethyl 4.65 39.6

Styrene 7.4 Anglamol 93 (E.P. Additive) 3.0 Amoco 9000 (Dispersant) 1.0Ultraphos ll, (Low Static Modifier) 1.0 Synthetic Sulfurized Oil ofExample 21 or 22 Th eUltraphos 11 additive is a surface-activejorganic'iia'ii n7 i "Mk-GM phosphate ester of a linear aliphatic, ethoxylatedalco- 5 The adamantane compounds containing such olefinic hol. Thehydrogenated poly(alphamethyl styrene) is terminal groups can beconverted to polar compounds primarily in the hydrindan form. A usefulfluid can also (as by the reaction of the examples) containing any of beformulated wherein the corresponding indan is subthe previouslydescribed functional groups. stituted for some or all of the hydrindan.The dicyclo- Example 25 hexyl alkane polymer forms are present as minorcon- I 3-Cyclohexyl-l ,1 ,3-trimethyl indan can be used as a stituentsof the hydrogenated poly(alphamethyl stytraction fluid base stockcomponent. The structural rene). Operable fluids can be made using up to100 formula of this compound is (1). percent of such dumbbell polymers.0 CH Other hydrocarbons which can be present in such H g traction fluids(in addition to the previously mentioned C OllS, e.g., hydrogenatedparaffimc or naphthemc lubes) HO 0 CH2 can be made by interaction (as byalkylation) of isobu- I tylene or polyisobutylene with napthenehydrocarbons (such as adamantanes, hydrindanes or cyclohexane). H 5 Suchisobutylene interaction products with adamang tanes are described inExample 24. H10 0112 Example 24 H2O CH2 Ethylaluminum sesquichloride(ml. of 25 vol Ip er ce nt 1;

solution) was added to a mixture of dimethyladamantane (50 ml.) andt-butylchloride (1 ml.). The mixture was maintained at 0-5C. whileisobutylene (45 g.) was added as a gas. The reaction was killed with 5ml. of water, extracted with water and distilled under vacuum. Thedistillation vessel was kept at 280C. to crack any high boiling product.The overhead was at about 170C. About half of the oil was cracked inthis manner, the rest distilled without cracking. About 30 ml. of oilwas obtained. It had KV of 4.40 es. and VTF-Vl of 26. A similar run at-30C. gave about 20 ml. (nearly all cracked) having KV of 4.22 cs. andVTF- V] of 62. Infrared spectroscopic analysis indicated that theadamantanemoiety was present in the product oil. This oil is useful as atraction fluid or as a component of a traction fluid. The structure ofone of the more important components of such a fluid is the following:

or one of the olefinic terminal groups prefiou sly re ferred to underthe heading Summary of the Inven- This compound was prepared m5iTiie'rsteel, rocker 'bomb which was charged with solid a-methylstyrene,100 g. indan dimer (3-phenyl-l,1,3-trimethylindan), and 2 g. 5%rhodium-on-carbon catalyst (Englehart lndustries). The bomb was chargedwith l fllm psig. hydrogen and heated to 100C. The pressure dropped to400 psig. after 1.5 hours. The bomb was cooled and the contents mixedwith pentane. The pentane solution was passed through a silica gelcolumn (2 ft. X 2 in.) and eluted with more pentane. The first twofractions (9 g. total) were the fully hydrogenated hydrindan derivative.The next 5 fractions contained 80 g. of the above compound I. About 10g. of unreacted starting material was recovered by further elution. Thestructure of I was determined by a combination of infrared analysis, NMRspectoscopy, and mass spectrometry. The purity by VPC analysis was =80%.The oil had a KV o of 3.24 cs.; a KV a of 25.17 es. and VTF-Vl of-l39The 3-cyclohexyl-l,l,3-trimethylindan was tested for traction using theRexana Four Ball Tester. The torque value for this sample was 68 g. Thecorresponding value for the fully hydrogenated material (hydrindanderivative) was 70 g. The unhydrogenated sample has a torque value of 59g. The precision of a single value in this test is il-Z grams. Example26 l, l ,3-Trimethyl-3-( 2,2-dimethyl propyl) hexahydroindan can be usedas a component of hydrocarbon base stock for use in compounding alubricant for a traction or friction drive. This compound was readilyprepared by hydrogenation of the corresponding indan. This compound isespecially remarkable because of its low viscosity compared to thecorresponding com- 5.69 es. and a VTF-Vl of 2.

pound in the a-methyl styrene dimer series (KV about one-half as much)and its viscosity index which is much higher than the parent compound.The fully saturated and the aromatic version have about the sametraction properties.

1 ,1 ,3-Trimethyl-3-(2,2-dimethylpropyl) indan (80 ml.) prepared aspreviously described in Example 25 was placed in a 300 ml. rocker bombwith 2 g. 5% rhodium-on-carbon. The bomb was charged to 1,500 psig. withhydrogen and heated to 200C. After 6 hours the bomb was cooled and theoil removed and filtered. The crude product had a KV o of 1.86 cs.; a KyQBTSSI cs. and VTFVI of T08. Since there appeared to be a small amountof volatile material present (probably caused by cracking during thehydrogenation), the sample was topped to 60 at 0.2 mm. Hg pressure. Onlyabout 2-5 ml. of distillate was collected. The viscosity properties wereKV o R of l.9l c s. ;a Ky A 66611605.anJVTl Y T of 85. The samplecontained at least 60% cis-trans isomers of the structural The c ompoundwas tested for traction using the Roxana Four Ball Tester, modified toshow torque measurements. The torque for this sample was 65 g. Thecorresponding torque for unhydrogenated a-methylstyrene dimer is 59 g.The precision of the test is about il-Z g.

Example 27 400 ml. nitromethane and 300 ml. distilled isobutylene trimerwere placed in a one-liter flask and heated to 85C. 6 ml. of SnCl wereadded. Then 75 ml. of a-methylstyrene were added dropwise over 35minutes. The temperature quickly rose to 95C. and was kept there. Afterthe addition was complete, the mixture was stirred at 95C. for anadditional 10 minutes, then cooled to room temperature. The upper oillayer was separated and washed twice with water, the water layers beingdiscarded. The oil layer was dried over CaCl and distilled, and the 80ml. of product that boiled from 60100C. at 0.5 mm. Hg. pressure wasretained. The major component (about t60 vol. was identified as II] by acombination of infrared, NMR, and mass spectroscopy. It had a KV o R of1.65 cs.; a KV F, of

11 cm on:

on, CH3

CH CH3 III The same compound could be made using diisobutylene.

dimer. The following equilibrium is probably involved:

Stannic chloride in nitromethane under certain condi tions will rapidlypolymerize some olefins, but not isobutylene oligomers (indeed, not mostolefins, including polar olefins, such as methylmethacrylate). Styrene,a-methylstyrene, isoprene, butadiene, isobutylene, 2- methylbutene-l areolefins that can be polymerized. If the a-methylstyrene cation can begenerated in the presence of a large excess of the other olefin,addition should be the predominant reaction. Running the reaction underconditions known to give the indan dimer with a-methylstyrene producessubstituted indans. The compound of this example has a remarkably lowviscosity and high viscosity index compared to the correspondinga-methylstyrene dimer derivatives.

The compound was tested for traction using the Roxana Four Ball Tester.The torque for this sample was 63 Table Ill presents Roxana Four BallTorque data for a number of polar compounds previously described herein.

Table IV presents the structural formulae of a number of cyclic polarcompounds which are useful as components of lubricants for a tractiontransmission or a friction drive. These components are especially usefulwhen present in the range of about 0.5 to 10 weight percent in a baselubricant comprising at least one fully or partially hydrogenated oilselected from polymers of styrene (or of substituted styrene, such asa-methylstyrene), polyolefins, naphthenic and paraffinic lubes. Suchpolar compounds can also be used in such lubricants which also containfrom 0.1 to percent of the gem-structured polar compounds previouslyreferred to herein. Sebacate esters (such as dioctyl sebacate or dibutylsebacate) can be used as polar components (in the 0.5 to 10 weightpercent range) of lubricants (as those referred to above) for a tractionor friction drive. For example, up to about 7 volume percent of suchesters can cause a significant increase in the traction coefficient ofthe blend of hydrocarbon base oils dis closed in Example 23 hereof, orin the entire lubricant composition disclosed in Example 23.

The ozone treatment described in Example 2 can also be used to improvethe initial and aged (with copper ASTM Dl923-B) power factors ofhydrorefin'ed mineral oils, used as electrical hydrorefined naphthenicoils having a SUS viscosity in the range of 4020,000 SUS at F. ForExample, a 2000 SUS (at 100F) hydrorefined (625F, 1000 psig of 100percent H 0.3 LHSV, sulfided Ni, Mo oxides on Al O naphthenic distillatewas contacted with 0.5 weight percent ozone to produce a dark coloredoil which, after 96 percent H 80 treatment, washing, neutralizing andadsorbent contacting (to remove the dark products). produced a goodcable oil.

Methods for analysis of the branched olefin and paraffin oils describedherein (as in Example 1) can be found in J. Poly. Sci, part A-l volume9, pp. 717-745 (March 1971).

Example 28 Nitromethane (200 ml.) and SnCl, (5 ml.) are stirred in athree-necked, round-bottomed flask (500 ml.) equipped with a gas inlettube, mechanicall stirrer, reflux condenser, external bath andthermometer, while isobutene is passed into the mixture kept at 36 C.The isobutene is feed to the flask at a rate sufficient to maintain noflow on the outlet side after air has been swept from the flask. After26 minutes the isobutene flow is stopped and the contents of the flasktransferred to a separatory funnel. Conversion of the isobutene isquantative. After allowing 5 minutes for phase separation, thenitromethane layer (202 ml.)is drained from the bottom of the funnel.The oil layer (235 ml.) is washed twice with saturated aqueous sodiumchloride solution, once with 5 percent aqueous sodium chloride solutionand twice more with saturated aqueous sodium chloride solution. The oillayer is then dried over anhydrous calcium chloride and placed in avacuum istillation apparatus. It is distilled to remove all materialboiling below 80 at 0.5 mmHg. The remaining oil fraction (100 ml.) has"the followingiiidfifiififiTWiEk. 5 4.25 cs, KV, 22.42 cs. VTF-VI= 98AST- M-Vl 104. The distillate (100 ml.) was approximately (by VPC) 49percent trimer and 49 percent tetramer. Any dimer would have been lostto the trap ml.). The loss on batch drying is about 30 ml.

* as used herein KV stands for Kinematic Viscosity as determined by ASTMD 445 Example 29 Example 28 was repeated except that the oil wasdistilled, collecting as the oil fraction the portion boiling from 80 to200C. This had the following properties: KV c F 3.23 cs, KV a F 14.09cs, VTF-Vl 105, ASTM-VI 104. This illustrates that the high viscosityindex of the product is not due to a wide blending range of productmolecular weight.

Example 30 A polymerization is carried out as in Example 28 except thatthe reaction temperature is maintained at 25C. Again, 235 ml. of productis obtained in 26 min. The distillation gives 33 ml. of low boilingdistillate (40 percent trimer, 57 percent tetramer) and 188 ml.remaining oil. This oil is percolated through about 12 in. of a columnpacked with activated alumina. The resulting oil is completely clear andhas the following properties: Kvz o F CS, Kv oo F CS, VTF-Vl 96, ASTM-VI96.

Any of the polyolefin oils of the present invention can be partially orfully hydrogenated by known methods (e.g., palladium on charcoalcatalysts, 2,500 psi hydrogen, at 274C) to improve their stability. Thepolyolefin oils or hydrogenated oils can be fractionally distilled undervacuum at from 40 to 250C. Distillate fractions covering the completeboiling range can be taken as feed stocks from which individualhydrocarbon species (olefins or paraffins) can be recovered,

The major branched hydrocarbon species of the distillate fractions canbe separated and isolated into chromatographic fractions of reasonablyhigh purity by linear temperature programmed and isothermal gaschromatography. In most cases, chromatographic fractions representativeof a single molecular species of each carbon number can be obtainedusing silicone rubber columns under isothermal conditions ranging from210 to 280C. In certain instances fractions consisting of hydrocarbonshaving several different carbon numbers have been prepared using suchcolumns. These concentrates can then be rechromatographed overanalytical columns and pure chromatographic fractions of single carbonnumber species collected.

Example 31 A polyisobutylene oil was prepared by thoroughly vacuumcracking commercial polyisobutylene (having a number average molecularweight of 23,000) in a stirred, round bottom flask at about 375C and 1mm. Hg. The product was taken overhead continuously with essentially noreflux or fractionation. The distillate products and traps were combinedand redistilled at C at 0.3 mm. Hg and the more volatile distillatefractions discarded. The remaining less volatile, thermally crackedpolyisobutylene bottoms fraction, which represented about 35 to 40percent of the total charge, can be used as an olefin oil to make polarcompounds, as in the reactions of Examples 2, 5 to 19, 21 and 22.Fractions, as by nondistructive distillation, of such bottoms can alsobe used to make such polar compounds.

Example 32 The thermally cracked" polyisobutylene oil of Example 29 washydrogenated in a 1 liter stainless steel hydrogenation reactor at 2,500psi hydrogen and 274C for 6 hours. The catalyst was 0.5 percentpalladium on 4 to 8 mesh coconut charcoal.

A gas chromatogram of the hydrogenated, thermally crackedpolyisobutylene contains a series of peaks which represent a homologousseries of two different basic classes of branched hydrocarbons. Oneclass is symmetrical, has an odd number of carbon atoms, and isterminated with two isopropyl groups. The second species isnon-symmetrical, consists of an even number of carbon atoms, and isterminated with an isopropyl group and a tertiary butyl group. Theincremental increase of carbon number for each series is due to anadditional C isobutylene, unit in the hydrocarbon chain. No significantamounts of the odd carbon numbered species which are terminated with twotertiary butyl groups were found to be present in these nonvolatilefractions. In the C to C range, the concentrations of the C and Cspecies were much lower relative to the concentration of higher carbonnumbered species, probably due to the loss of a portion of thesehydrocarbons to the volatile fractions. The purity and molecular weightdata obtained for each collected hydrocarbon species, C to C are givenin Table l. The purity of these fraction varied from 96.7 to 99* percentand the calculated molecular weight of each carbon number species was ingood agreement with the experimental molecular weight value obtainedusing vapor pressure osmometry.

The identity of these branched hydrocarbons, as determined by MNRspectroscopy, are indicated by the structural assignments shown in J.Poly. Sci, part A-l Volume 9, pp. 717 to 745 (March, 1971). The observed resonance positions in CC], and assignments for the methylene andmethyl protons of this series of hydrocarbons are summarized in theabove paper. Methyl and methylene protons of the same type and havingthe same degree of steric hinderance and crowding" were found to haveessentially the same chemical shifts in CCl for each individualhydrocarbon species regard less of carbon number. Differentiation andassignment of a number of the maximally crowded methylene and maximallycrowded geminal dimethyl groups in these compounds was possible fromIOQ-MI-Iz spectra obtained using C D solvent. The observed protonresonance positions for these groups in C D and their assignment in theC to C hydrocarbon species are summarized in the above paper.

Table II gives the refractive indices determined at 25C for the C to Chydrocarbon species. These values are compared with the calculatedvalues obtained for these compounds using the Greenshields and Rossinimethod. The difference in refractive indices, ARI, (calculated minusexperimental) was found to increase with increasing carbon number.Included also in this table are density values which were obtained fromthe calculated molal volumes (25C) of these hydrocarbon species and twoexperimental density values which were determined for the C and Cspecies. Positive deviations between calculated and observed densityvalues were found for the C and C hydrocarbon spe- .cies.

Substantially pure olefin species can be obtained and characterized in asimilar manner from the unhydrogenated polyisobutylene oils.

The novel branched paraffin and olein hydrocarbon species arecharacterized by crowded and sterically hindered methyl and methylenegroups. This crowding effect, although somewhat less pronounced in thelower carbon number species, becomes significantly greater with anincrease in the carbon chain. The introduction of methylenes between twointernal geminal methyl groups or between an internal geminal methyl anda t-butyl group (a to each group) causes significant bending of thehydrocarbon chain. This bending results in much greater crowding andsteric hinderance of the various protons which in turn restrict freerotation of the individual methylene and geminal methyl groups.Resulting anisotropy changes cause a downfield chemical shift of theirproton resonance signals.

The lower limit of this downfield shift in branched paraffins (CCIL,solutions) is 66 Hz (1.10 ppm) for internal geminal methyls and 85 Hz(1.42 ppm) for isolated methylenes. This occurs in the polymer,polyisobutylene; where the repeating isobutylene unit provides maximumcrowding of both the geminal methyl and the isolated methylene groups.The lower carbon number, C C and C branched hydrocarbon species have nomaximally crowded geminal methyl groups.

The C hydrocarbon species is characterized by having both crowded andmaximally crowded geminal methyl groups. This is the first molecularspecies in this series of compounds which has maximum crowding" of ageminal methyl group. A geminal methyl group has maximum crowding whenit is l adjacent, a, to two isolated methylene groups and (2) beta, B,to two quante'rnary carbon atoms. This crowding is comparable to themaximum crowding of geminal methyls of high molecular weight (e.g.,200,000+) polyisobutylene. The resonance signal for the maximallycrowded" geminal methyl, like the resonance signal for the maximallycrowded geminal methyls of polyisobutylene, is shifted downfield andappears at 65-66 Hz (I.O8l.l0 ppm). The two isolated methylenes in thismolecule (referred to as the terminal isolated methylenes in the longercarbon chain species) are both adjacent to a maximally crowded" geminalmethyl group and are, therefore, more sterically hindered and crowdedthan the isolated methylenes of the C and C species. This increasedmethyl crowding causes a 5 Hz downfield shift of the methylene resonanceto Hz (1.33 ppm), where one single resonance peak is observed for bothisolated terminal methylene groups. These methylene groups are definedas crowded methylenes and are found in all of the higher carbon nubmerspecies (C and above).

The C hydrocarbon species is the only other compound in this serieswhich has a single maximally crowded" geminal methyl group. Thismolecular species, which is symmetrical about the maximally crowdedgeminal methyl group, has two isolated methylenes, having exactly thesame molecular environment. These groups are, therefore, magneticallyequivalent. The NMR spectrum of the C species in both CCL, and C Dsolvents show a single proton resonance peak for these crowdedmethylenes. All of the odd carbon numbered species in this series arecharacterized by this molecular symmetry and have terminal isolatedcrowded methylene groups which are identical. The unsymmetrical Chydrocarbon species is the first species of this hydrocarbon serieswhich has a maximally crowded methylene group. An isolated methylenegroup has maximum crowding when it is adjacent to, or between, twomaximally crowded geminal methyl groups such as in polyisobutylene.

The subsequent higher carbon numbered novel hydrocarbons (C23 to C havean increasing number of maximally crowded geminal methyl and maximallycrowded methylene groups, and consist of two basic species (1) and oddcarbon numbered species terminated with two isopropyl groups andsymmetrical about either a maximally crowded geminal methyl group or amaximally crowded methylene groups and (2) an even carbon numberedspecies terminated with both an isopropyl and t-butyl group and withouta center of symmetry. The C and C species are illustrated below where Arefers to maximally crowded geminal methyl groups and B corresponds tomaximally crowded methylene groups.

Integrated intensities of the observed resonance for each carbon numberspecies were consistent for the theoretical number of maximally crowdedmethylenes and maximally crowded" geminal methyls predicted for eachassigned structure. The number of maximally crowded methylene groups isalways one less than the number of maximally crowded" geminal methylgroups. Further details of the characterization of compounds containingside groups can be found in the J. Poly. Sci. paper.

TABLE I Purity and Molecular Weight Data for Collected FractionsMolecular Weight CROSS REFERENCE TO RELATED APPLICATIONS 1n commonlyowned copending application Ser. No. 52,301, filed July 6. 1970, of GaryL. Driscoll. lrl N.

5 Duling and David S. Gates. novel polyolefin and hydro- Carbon Relativet Purity calculated Observed, Em, genated polyolefin 011s are described\1h1ch are usetul as traction flu1ds, or as components of tractionflu1ds. 3+ 23-; 161 In particular, said application discloses oilsconsisting :2 3 1 essentially of isobutene oligimers in the C, C carbor116 99+ 226.4 219 -2.8 number range. The novel polyolefin 011s or the1nd1v1d- $3 33: ual olefins therein are also disclosed as being usefulas 23 96.7 324.6 322 ().8 chemical intermediates to prepare novel polarcompo- 33 333-9 3;; 1-3 nents (such as alcohols, acids, esters, ketones,thioke- 5 4 5 5 tones, amides, amines, thioesters, phosphate esters of31 3g? 29-: 426 the alcohols and th1oesters). The ketones, and other 324 t. 444 1.5 35 973 4929 490 non-ac1d1c ozonolysls products aredisclosed as be ng 36 99+ 507.0 513 +1.2 useful as tract1on fluids or ascomponents of tract1on 39 99+ 549.0 544 -0.9 40 99+ 570 +11 fluids. Saidappl1cat1on also contams a declaration that such derlvatlves, and thenuse as traction flu1ds or as aCupiHarygaschromawgraphyantiwear additivesin lubricants are the invention of hVupor pressurcosmometry. GaryDl'iSCQll and Marcus Haseltine, JR, the

TABLE I] present applicants.

Physical Property Data Refractive Index R1 Calculated" CarbonCalculated" Observed ARI Density No. (C) (25C) (Cale-obs.) (25), g/cc 3See Greenshields and Rossini. From calculated value of molal volume at25C. Observed value= 0.8584 g/cc. d Observed value= 0.8631 g/cc.

TABLE 111 ROXANA 4-BALL TESTING Traction Running (grams of VTF SampleDesignation Time torque) KV KV V1 Scar 1. P18 (Starting material) 73.34.49 24.14 101 Med 92 min 72.8 1 min 73.9 2. PlB-Kctonc (Batch 1) 83.23.97 21.14 88 Med.

(Oxidativc Work-Up) min 82.5

1 min 84.0 3. PlBKetone (Batch 1) 84.4 (See No. 2) Med.

(Oxidative Work-Up) 72 min 83.0 1 min 85.8 4. PlB-Kctone (Batch 1) 83.8(See No. 2) Med.

(Oxidativc Work Up) 92 min 82.5

1 min 85.2 1% min 85.9 2 min 86.9 5. PlB-Ketone (Batch 2) 75.9 Med.

(Oxidutive Work-Up) min 73.9 1 min 77.8 1% min 82.8 2 min 85.5 6.PlB-Kctonc (Batch 2) 74.0 Med.

(Oxidativc WorkUp) ,2 min 71.4 1 min 76.5 1% min 80.5 2 min 82.3

TABLE I11 Continued ROXANA 4-BALL TESTING Traction Running (grams of VTFSample Designation Time torque) KV KV V1 Scar 7. PlB-Ketone (Batch 2)77.5 Med.

(Oxidative Work-Up) V: min 71.5 1 min 83.5 1% min 85.5 2 min 89.2 H.PlB-Ketone (Hydrnlytic 72.6 Med.

Work-Up) V: min 71.9 1 min 73.4 9. PlB-Ketnne (Hydrolytie 71.3 SlightWork-Up) A: min 70.9 1 min 71.7 1% min 72.3 2 min 73.5 10. PlB-Ketone(Hydrolytic 74.6 Very Work-Up) Composite A min 74.5 Slight 1 min 74.7 1%min 75.2 2 min 75.4 11. PlB-Ketone (Hydrolytic 74.2 Very Work-Up) (MetalCatalyst) 1: min 74.2 Slight l min 74.1 1 min 74.9 2 min 75.4 12.PlB-Kctonc (Hydrolytic 7l.9 Slight Work-Up) (High Temp.) 7% min 71.5 1min 72.2 1% min 73.0 2 min 74.3 13. L-IO-Kctone (Hydrolytic 63.0 6.8657.8 67 Med Work-Up)(1ndopo1Po1y- 6 min 63.0 butene) l min 62.9 14.L-lO-Ketone 70.8 Large 6 min 67.6 l min 73.9 1% min 77.9 2 min 78.5 2%min 79.9 15. L-IO-Kctone 72.1 (See N0. 14) Large 96 min 68.7 1 min 75.5l 1% min 76.3 2 min 77.5 16. P11i(Ketone/Acid) 75% 75.5 Med.

(25% P18) 16 min 74.8 1 min 76.2 17. FIB-Acid 74.0 17.51 377.9 25 SlightA min 73.9 1 min 74.2 18. P1B-A1c0h01(75%) 70.8 Very (25% P113) 6 min69.9 Slight 1 min 71.8 19. PlB-Ester I 81.4 Ex

1% min 80.6 tremely l min 82.2 Slight 20. PIE-Ester 10% K0880* 71.7 Veryh min 71.9 Slight l min 71.6 21. P1BBr 69.1 Very A min 69.] Large l min691 22. 40 PlB-Ketone 77.2

60 Polybutene 6 min 76.5 1 min 78.0 23. N0. 22 12% K0880 68.5 Slight '22min 68.6 1 min 68.4 24. I0 P|B-Ketone 66.6 Large 90 H.P.O.*" 15 min 65.5Scar l min 67.7 H.P.O.** 57.9 3.99 20.51 96 Large 6 min 57.7 1 min 58.2Polybutene' 67.5 3.34 16.36 82 Med.

1% min 67.7 1 min 67.2 PAM VCH 75.4 6.83 97.87 72 Med.

'6 min 74.7

l min 76.2 l'ri min 75.9

2 min 76.2

' K0880 is a typical commercial additive package for use in conventionalautomotiv [or EP. antioxidant. antirust. dispersant. antieoppercorrosion and antifoam.

" Hydrogenated paralfinic oil PAMVCH a hydrogenated dimerizate ofa-methylstyrene, mainly the hydrindan form. Med." is an ahhreviation forMedium."

NB. All percentages in the above table are by volume Said applicationfurther declares that the processes for preparation of said ozonolysisproducts are the invention of Gary L. Driscoll. One such process,disclosed in said application, involves mixing the polyolefin oil withabout 3 volumes of acetic acid or methanoland adding ozone thereto. Thereaction can be effected in the range of 80-l00C. (preferably 80C.). The

TABLE I'v' POLAR TRAO'IANTS HaC CH:

amount of ozone can be about one molecule of ozone per each double bondin the oil. After reaction of the double bond with the ozone, an excessof water or hydrogen peroxide is added to hydrolyze the ozonolysisproducts. About 1 volume of water per volume of oil is sufficient toproduce a mixture comprising acids and ketones.

The invention claimed is:

1. In a friction or tractive drive comprising at least two relativelyrotatable members in torque transmitting relationship, the improvementwherein the tractive surfaces of said members have disposed thereon afluid tractant composition containing from 1.0 to I00 weight percent ofat least one polar compound having the structural formula:

' L CH:

clohexyl, indanyl, hydrindanyl, cyclohexylindanyl andcyclohexylhydrindanyl and where Y is selected from;

(1) (il) (iii) and wherein R and R are C alkyl, or saturated, olefinicunsaturated or aromatic cyclic or alkyl-substituted cyclic hydrocarbons;and R and R are hydrogen or R and wherein each of R, R R and R when onthe same molecule, may be the same or different, the balance of saidcomposition comprising a hydrocarbon oil of lubricating viscosity and anadditive in lubrication improving amounts selected from the groupconsisting of extreme pressure, antioxidant, antirust, dispersant,anticopper corrosion and antifoam.

2. A drive according to claim 1 wherein y is O -iL -OH a vapor phasechromatogram of said composition in the C to C carbon number regionshows nearly base line resolution and is free of any significantenvelope and peaks produced by oxygenated hydrocarbons which do notcorrespond to said formula.

3. A drive according to claim 2 and containing a hydrocarbon base stockcomprising from 15 to VOL ume percent of at least one member from thegroup consisting of paraffinic oils, naphthenic oils, olefin homopolymeroils, olefin copolymer oils and said oils which have been at leastpartially hydrogenated.

4. Drive of claim 1 containing oil consisting essentially of at leastfour structurally different members selected from at least one of thegroups (A) or (B) wherein (A) is a branched olefin hydrocarbon having16, 20, 24, 28, 32, 40, 44 or 48 carbon atoms and (B) is a branchedparaffinic hydrocarbon having 16, 20, 24, 28, 32, 40, 44 or 48 carbonatoms, said hydrocarbon having the formula:

wherein n is an integer from 3 to ll in clusive, and wherein Z is:

when said hydrocarbon is a paraffin, and Z is:

when said hydrocarbon is an olefin and wherein said oil contains from0.1 to 10 weight percent ofa polar compound as defined in claim 1.

5. A drive according to claim 1 wherein said polar compound has thestructural formula Clix l CHa-( CH2( J a. L and.

where in is o R o -fi-H, -0- R;, or J-0-i'i-Ra,

w hereiii'n is 1 to 17f 9. A drive according to claim 8 and containing ahydrocarbon base stock comprising from to 100 volume percent of at leastone member from the group consisting of paraffinic oils, naphthenicoils, olefin homopolymer oils, olefin copolymer oils and said oils whichhave been at least partially hydrogenated.

10. The drive as defined in claim 8 and wherein when Z is (f) or (g), nis an integer from 2 to 16 and when Z is (c), n is an integer from 3 to17.

11. A drive according to claim 5 wherein a vapor phase chromatogram ofsaid compo t ion in the C to C carbon number region shows nearly baseline resolution and is free of any significant envelope and peaksproduced by oxygenated hydrocarbons which do not correspond to saidformula.

12. A drive according to claim land containing a hydrocarbon base stockcomprising from 15 to volume percent of at least one member from thegroup consisting of paraffinic oils, naphthenic oils, olefin homopolymeroils, olefin copolymer oils and said oils which have been at leastpartially hydrogenated.

13. A drive according to claim 1 wherein Y is wfl rnw a -i?-OH 14. Adrive according to claim 1 wherein Y is 1 5. according to claim 1wherein Y is ELL;

2. A drive according to claim 1 wherein y is
 3. A drive according toclaim 2 and containing a hydrocarbon base stock comprising from 15 to100 volume percent of at least one member from the group consisting ofparaffinic oils, naphthenic oils, olefin homopolymer oils, olefincopolymer oils and said oils which have been at least partiallyhydrogenated.
 4. Drive of claim 1 containing oil consisting essentiallyof at least four structurally different members selected from at leastone of the groups (A) or (B) wherein (A) is a branched olefinhydrocarbon having 16, 20, 24, 28, 32, 40, 44 or 48 carbon atoms and (B)is a branched paraffinic hydrocarbon having 16, 20, 24, 28, 32, 40, 44or 48 carbon atoms, said hydrocarbon having the formula:
 5. A driveaccording to claim 1 wherein said polar compound has the structuralformula
 6. The drive as in claim 1 and wherein n is an integer of from 3to
 20. 7. A drive according to claim 5 and containing a hydrocarbon basestock comprising from 15 to 100 volume percent of at least one memberfrom the group consisting of paraffinic oils, naphthenic oils, olefinhomopolymer oils, olefin cOpolymer oils and said oils which have been atleast partially hydrogenated.
 8. A drive according to claim 1 wherein atleast one of said polar compounds has the formula
 9. A drive accordingto claim 8 and containing a hydrocarbon base stock comprising from 15 to100 volume percent of at least one member from the group consisting ofparaffinic oils, naphthenic oils, olefin homopolymer oils, olefincopolymer oils and said oils which have been at least partiallyhydrogenated.
 10. The drive as defined in claim 8 and wherein when Z''is (f) or (g), n is an integer from 2 to 16 and when Z'' is (c), n is aninteger from 3 to
 17. 11. A drive according to claim 5 wherein a vaporphase chromatogram of said composition in the C15 to C50 carbon numberregion shows nearly base line resolution and is free of any significantenvelope and peaks produced by oxygenated hydrocarbons which do notcorrespond to said formula.
 12. A drive according to claim 1 andcontaining a hydrocarbon base stock comprising from 15 to 100 volumepercent of at least one member from the group consisting of paraffinicoils, naphthenic oils, olefin homopolymer oils, olefin copolymer oilsand said oils which have been at least partially hydrogenated.
 13. Adrive according to claim 1 wherein Y is
 14. A drive according to claim 1wherein Y is
 15. A drive according to claim 1 wherein Y is